EP2113522A1 - Method for creating a colour master batch, colour master batch and polymer material coloured with same - Google Patents

Method for creating a colour master batch, colour master batch and polymer material coloured with same Download PDF

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Publication number
EP2113522A1
EP2113522A1 EP08008303A EP08008303A EP2113522A1 EP 2113522 A1 EP2113522 A1 EP 2113522A1 EP 08008303 A EP08008303 A EP 08008303A EP 08008303 A EP08008303 A EP 08008303A EP 2113522 A1 EP2113522 A1 EP 2113522A1
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Prior art keywords
carbon atoms
radical
polymer
fluorine
independently
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EP08008303A
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German (de)
French (fr)
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EP2113522B1 (en
Inventor
Friedhelm RÖBER
Dietmar Dr. Chmielewski
Hans-Joachim Prof. Dr.-Ing. Radusch
Matthias Hübner
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DAW SE
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DAW SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the present invention relates to a process for the preparation of a color masterbatch based on a thermoplastic silicone copolymer. Furthermore, the invention relates to a corresponding color masterbatch. Such color masterbatches are used in the coloring of polymer materials.
  • Color masterbatches are currently typically made from plastic granules and colorants. For this purpose, a separate industry has been formed on the market, which has specialized in it. The coloration is carried out by mixing and melting of colorant and plastic granules with the addition of small amounts of additives in twin-screw extruder. Both single-stage and two-stage masterbatch production are practiced. While In the single-stage production, all raw material components are initially charged and extruded, the two-stage production leads to so-called “mono-concentrates", which are mixed again in the second step and optionally provided with additives and extruded. The homogeneity of the hue in the plastic depends on which flow behavior is achieved in the melt or how well the masterbatch spreads in the matrix. There are therefore special types of masterbatches for every plastic class.
  • a principal problem of masterbatch production is that pigments whose primary particles are in the size range of a few nanometers to a few micrometers must be incorporated into the macromolecular materials in the melt-mixing process.
  • the digestion of the pigment aggregates and agglomerates and the homogeneous distribution of the pigments in the z.T. very high-viscosity plastic melt can be quite problematic.
  • an already melted and granulated polymer material must be remelted during this melt compounding and granulated. This depends on the procedure even up to twice.
  • the repeated thermal stress can also lead to damage of the masterbatch support material as a result of chain degradation reactions resulting in molecular weight degradation.
  • a particularly interesting plastic which covers a wide field of application due to its advantageous material properties, is an organopolysiloxane / polyurea / polyurethane block copolymer, which is described in US Pat EP 1 489 129 A1 is disclosed.
  • the polymer formation in step b) is preferably carried out at temperatures of at least 20 ° C. In principle, however, it is also possible to work at low temperatures.
  • the interference of the colorants can be carried out according to the invention in the liquid precursors of the siloxane copolymers.
  • the homogeneous dispersion of large concentrations of colorants in these relatively low-viscosity systems is easy to handle and easily implemented by the techniques established in the paint and coatings industry.
  • the problem of mixing the colorant in the liquid precursors of the polysiloxane copolymers is by no means triviallibrarytun.
  • polymer materials are built up from monomers with very low molecular weights. These monomers are either gaseous or liquid, with very low viscosities.
  • the colorant incorporation in polymeric precursors, ie in the monomers is therefore not possible for most polymers or can only be realized with a very large technical outlay.
  • the advantage of the polysiloxane copolymers is that the basic components are not monomers in the classical sense, but rather oligomers.
  • the organosilicon compound can be distinguished by molar masses of> 10,000 g / mol. Therefore, one has it with the basic components of the polysiloxane copolymers to do with easy to handle fluids. In the field of polymer synthesis, therefore, the incorporation of colorants in a fluid precursor may already be considered an innovation.
  • the fluid precursors it is possible to produce pastes with the basic shades. These pastes can be mixed to final shade before polymer synthesis. By subsequently reacting the components to the finished color masterbatch, the product is obtained in only one extrusion step.
  • the major advantage is that the carrier material of the color masterbatch is only subjected to thermal stress once before the end use. This reduces the influence of thermal degradation reactions on the matrix.
  • a further advantage of the process according to the invention is that, after the dispersion of the colorants into the fluid polymer precursor, there is a further dispersion and homogenization of the colorants in the reacted polymer matrix in the extruder. This additionally improves the colorant distribution in the color masterbatch.
  • the colorants used are preferably pigments, dyes or mixtures thereof.
  • Suitable pigments are both inorganic and organic pigments.
  • the inorganic pigments include those of the group of oxides, for example iron oxide (brown, red, black), chromium oxide (green), titanium dioxide, or carbon, for example carbon black, or chromates, for example lead chromate, molybdate orange, or complexes of inorganic colored pigments , eg chrome titanium yellow, chrome iron brown, cobalt blue, nickel titanium yellow, Zinc iron brown, bismuth vanadate yellow, or sulfides, eg cadmium sulfide (yellow, orange, red), cerium sulphide (yellow, orange, red), ultramarine (purple, blue), zinc sulphide (white).
  • oxides for example iron oxide (brown, red, black), chromium oxide (green), titanium dioxide, or carbon, for example carbon black, or chromates, for example lead chromate, molybdate orange, or complexes of inorganic colored pigments ,
  • the organic pigments include azo pigments, eg laked azo pigments (yellow, red), disazo pigments (yellow, orange, red), disazo condensation pigments (yellow, red), benzimidazole pigments (yellow, orange), metal complex pigments (yellow), insoindoline pigments (yellow), insoindolinone pigments (yellow), or also polycyclic pigments, eg quinacridone (violet, blue), quinophthalone (yellow), diketo-pyrrolo-pyrrole (orange, red, violet), disoxazine pigments (violet), indanthrone (blue), perylene (red, violet ), Phthalocyanine (blue, green).
  • azo pigments eg laked azo pigments (yellow, red), disazo pigments (yellow, orange, red), disazo condensation pigments (yellow, red), benzimidazole pigments (yello
  • Dyes include both soluble dyes, e.g. Anthraquinone, quinophthalone, pyrazolone, perinone and monoazo dyes, as well as fluorescent dyes, e.g. Perylene, naphthalimide, cumin derivatives, thioindigo, thioxanthene benzanthrone in question.
  • fluorescent dyes e.g. Perylene, naphthalimide, cumin derivatives, thioindigo, thioxanthene benzanthrone in question.
  • the invention likewise provides a color masterbatch which can be produced by the method described above.
  • the color masterbatch according to the invention which can be prepared by the method according to the invention, exhibits excellent homogeneity, ie no concentration gradient of the colorant in the masterbatch.
  • Further advantageous properties of the color masterbatch include high tensile strength, high thermal stability, excellent stress-strain behavior or rheological behavior, and excellent permeation behavior for a large number of substances.
  • the color masterbatch proves to be very tolerant of a large number of plastics with which good compatibility is possible in the usual concentrations for plastics processing and modification.
  • a decisive advantage of the color masterbatch in connection with other plastics is the better flow behavior of the matrix in the melt, whereby particularly complicated injection molded parts experience a better and faster injection mold loading and thus a higher economic efficiency is given.
  • Another important advantage of the color masterbatch is that it can achieve an enormous increase in throughput in extrusion applications.
  • the polysiloxane copolymers used according to the invention consist, as already described, of two or three components of the siloxane structure A and the organic components B and optionally C. These copolymers are generally of the type AB alternating block copolymers (consisting of at least two block sequences ) or type ABA (consisting of three blocks). These polymers are formed either by polyaddition reaction or polycondensation reaction with elimination of eg water. For the formation of these polymers, two bifunctional components are generally required. On the one hand, a bifunctional component A, which contains an organic silicon compound and, on the other hand, a bifunctional component B. The functional groups of component B must be such that they are able to react with the functional groups of component A. Are component A and component B in stoichiometric ratios, ie in the molar Used ratio 1: 1, formed under certain reaction conditions and optionally with the addition of a catalyst long macromolecules in which component A and component B alternate.
  • a third component C which is also referred to as a chain extender, is incorporated in these polysiloxane copolymers.
  • the reaction to the macromolecule is usually carried out in two stages, wherein the one-step process is possible. First, component A and component B are reacted again. However, the stoichiometric ratio of A and B is chosen so that only defined short molecules with the exact structure BAB are formed. The molar ratio of A to B here is 1: 2.
  • Component C is also bifunctional and the functional groups of component C are capable of reacting with the functional groups of component B. In a second, later reaction step, the addition of the component C.
  • the siloxane structure A is highly non-polar in the copolymer.
  • the organic components B and C introduce polar groups into the copolymer.
  • the polysiloxane copolymers can be adapted to a wide variety of polymer materials in terms of compatibility. The result is that one or only a few basic materials can be used to produce color masterbatches for almost all polymer materials.
  • the color masterbatch In addition to the universal applicability is a further advantage of the color masterbatch that the polymer is not only dyed, but that the color masterbatch support material, ie the polysiloxane copolymer, simultaneously acts as a processing aid.
  • the cycle times can be significantly reduced while the process parameters in the injection molding process are otherwise constant. In the extrusion process, the throughput can be increased significantly under otherwise constant conditions. This means in all cases an improvement in the economics of the process.
  • thermoplastic elastomers are among the thermoplastic elastomers, these materials can act as toughening modifiers for other thermoplastic materials in special cases. In addition to dyeing and improved processability, it is thus also possible to achieve further effects, such as toughness modification, by means of this color masterbatch.
  • the siloxane structure is non-polar.
  • the siloxane sequences of the copolymers attach to the surface of the modified polymeric materials.
  • particularly polar materials such as PET or PA, are polar shielded on the surface, that is, they are made non-polar.
  • surfaces can be highly water-repellent equipped.
  • the colorant may preferably be mixed into the not yet polymerized components or the corresponding mixtures thereof (before or during step a)), but as an alternative and / or additional process step it is also conceivable to use the colorant during the polymerization, i. to meddle before their conclusion (step b)).
  • the at least one colorant based on the weight of the polymer formed, in an amount of 1 to 80 wt .-%, preferably 10 to 50 wt .-% is added.
  • the colorants are selected from the group consisting of pigments and / or dyes.
  • the bifunctional compound is selected from the group consisting of diisocyanates, diamines, diols, dicarboxylic acids, formaldehyde-terminated compounds, and mixtures thereof.
  • R 3 is an optionally substituted by fluorine or chlorine alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms.
  • a further preferred variant provides that immediately after step a) to the intermediate of components A and B at least one chain extender (component C) having the general formula III: HVR 4 -WH (III)
  • R 4 is an optionally substituted by fluorine, chlorine, C 1 -C 6 alkyl or C 1 -C 6 alkyl ester alkylene radical having 1 to 700 carbon atoms, in which non-adjacent methylene units by groups -O-, -COO- , -OCO- or -OCOO- may be replaced, and V, W independently of one another -O- or -NR 5 -, wherein R 5 is hydrogen, an alkyl radical having 1 to 10 C atoms or an aryl radical having 6 to 22 carbon atoms, is added.
  • diamines and diols in particular 1,4-butanediol, 1,6-hexanediol, ethylene glycol, 4,4'-methylene-bis (2-chloroaniline), are particularly preferred.
  • additives for example selected from nanofillers, stabilizers, antistatics, flame retardants, adhesion promoters, nucleating agents, blowing agents, antibacterial agents and mixtures thereof.
  • the amount of additives is preferably between 1 and 80 wt .-%, based on the weight of the polymer formed.
  • additives e.g. Nanofillers, stabilizers, antistatic agents, flame retardants, adhesion promoters, nucleating agents, blowing agents, antibacterial agents and mixtures thereof may be contained.
  • the amount of the additives is preferably 1 to 80 wt .-%, based on the weight of the polymer formed.
  • a colored polymer material containing the color masterbatch according to the invention is provided.
  • the color masterbatch has a high compatibility with a large number of polymer materials or blends thereof.
  • polymer materials or blends thereof include in particular polyethylene, polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, thermoplastic elastomers based on crosslinked rubber, ethylene-vinyl acetate, polyhydroxybutyrate and / or copolymers or blends thereof.
  • the color masterbatch may be based on polystyrene, impact-modified polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride, polymethyl methacrylate, polycarbonate, Polyaryletherketone, polyacrylonitrile, polyetherimide, polyethylene naphthalate, polyethersulfone, polyimide, polyketone, polyoxymethylene, polyphenylene sulfide, polyphenylene sulfone, polysulfone, styrene-butadiene rubber, acrylonitrile-butadiene rubber, natural rubber and their copolymers or blends.
  • the polymer materials are in particular produced by mixing at least one polymer material with the color masterbatch in the molten state and cooling the mixture.
  • the polymeric materials are in the form of a molded article obtainable by a molding process selected from the group consisting of injection molding, extrusion, compression molding, roll rotation, rotational molding, laser sintering, fused deposition modeling (FDM), granulation and / or casting.
  • a molding process selected from the group consisting of injection molding, extrusion, compression molding, roll rotation, rotational molding, laser sintering, fused deposition modeling (FDM), granulation and / or casting.
  • the color masterbatches were each prepared from a polyaddition reaction of aminopropyl-terminated polydimethylsiloxane (atPDMS) having an average molecular weight of 2700 g / mol and tetramethylxylene diisocyanate (TMXDI) and the addition of color pigments.
  • atPDMS aminopropyl-terminated polydimethylsiloxane
  • TXDI tetramethylxylene diisocyanate
  • a color masterbatch 40 g of the atPDMS were added to the laboratory kneader, which was preheated to 70 ° C. and running at 60 rpm. Subsequently, 18.7 g (corresponding to 30% by weight of the total formulation) of the inorganic pigment TiO 2 were added and mixed isothermally with the fluid atPDMS over a period of 300 s. In the following step, 3.6 g of the TMXDI were added. After 120 s isothermal reaction time, the kneader was heated to 180 ° C. at 20 K / min.
  • the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the inorganic pigment.
  • the color masterbatch matrix formed was in the melt state. After reaching the temperature of 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.
  • a color masterbatch 40 g of the atPDMS were added to the laboratory kneader, which was preheated to 70 ° C. and running at 60 rpm. Subsequently, 18.7 g (corresponding to 30% by weight of the total formulation) of the organic pigment phthalocyanine green pigment were added and mixed isothermally with the fluid atPDMS over a period of 300 s. In the following step, 3.6 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min.
  • the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer out.
  • the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.
  • a color masterbatch 40 g of the atPDMS were added to the laboratory kneader, which was preheated to 70 ° C. and running at 60 rpm. Subsequently, 43.6 g (corresponding to 50% by weight of the total formulation) of the inorganic pigment TiO 2 were added and mixed isothermally with the fluid atPDMS over a period of 300 s. In the following step, 3.6 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer.
  • the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.
  • TMXDI TMXDI
  • the color masterbatch was prepared by metering 40 g of the atPDMS into the laboratory kneader preheated to 70 ° C. and running at 60 rpm. Subsequently was added the paste produced in the first step. After 240 s isothermal reaction time, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer.
  • the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.
  • Preparing for the color masterbatch preparation 50% by weight of an inorganic cobalt pigment was homogeneously incorporated in a friction mill into the fluid atPDMS.
  • To prepare a color masterbatch 70 g of the paste were placed in the laboratory kneader running at 70 ° C. at 60 rpm. Subsequently, 3.2 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the colorant.
  • the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and then removed from the laboratory kneader and cooled to room temperature. Subsequent granulation gave a free-flowing, tack-free color masterbatch.
  • Preparing for the color masterbatch preparation were 40 wt .-% of an organic yellow pigment on a Grinding wheel homogeneously incorporated into the fluid atPDMS.
  • To prepare a color masterbatch 55 g of the paste were placed in the laboratory kneader running at 70 ° C. at 60 rpm. Subsequently, 2.6 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the colorant.
  • the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and then removed from the laboratory kneader and cooled to room temperature. Subsequent granulation gave a free-flowing, tack-free color masterbatch.
  • Embodiments 7-9 the base pastes described in Examples 5 and 6 were weighed in ratios of 20/80, 50/50 and 80/20 with a total weight of 65 g each. The pastes were then added to the laboratory kneader running at 60 ° C. at 70 ° C. and mixed for 120 s. Then the appropriate amount of TMXDI (2.68 g, 2.93 g, 3.16 g) was added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min.
  • the at PDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the different colorants.
  • the color masterbatch matrix formed was in the melt state. After reaching the 180 ° C, the system was mixed in the melt for a further 180 s and then taken from the laboratory kneader and cooled to room temperature. The resulting color masterbatches showed different shades of green depending on the mixing ratio of the base pastes (blue and yellow). Subsequent granulation gave a free-flowing, tack-free color masterbatch.

Abstract

Producing a color master batch (I) comprises: (a) mixing at least one amino-, hydroxyl- or carboxyl-group terminated siloxane structure (A) with at least one bifunctional compound (B); (b) forming a polymer mixture of components (A) and (B); and (c) melting the polymer in an extruder or batch mixers, followed by granulation, where at least one colorant is added to a liquid precursor of the polymer before the end of the polymer formation, to obtain polymer in the form a paste. Process for producing a color master batches (I) comprises: (a) mixing at least one amino-, hydroxyl- or carboxyl-group terminated siloxane structure of formula (X-R2-[-Si(R1) 2-O-] n-Si(R1) 2R2-) (A) with at least one bifunctional compound (B); (b) forming a polymer mixture of components (A) and (B); and (c) melting the polymer in an extruder or batch mixers, followed by granulation, where at least one colorant is added to a liquid precursor of the polymer before the end of the polymer formation, to obtain polymer in the form a paste. R1 : a monovalent 1-20C hydrocarbon optionally substituted by F or Cl; R2 : 1-20C alkylene, in which non-adjacent methylene units is replaced by O, or 6-22C arylene; X, Y1 : hydroxyl, carboxyl or amino group of formula (-NR1a-); R1a : H, 1-10C alkyl or 6-22C aryl; and n : 1-10000. Independent claims are included for: (1) the color master batch prepared by the process; and (2) a polymer material containing the color master batch.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Farb-Masterbatches auf Basis eines thermoplastischen Silikoncopolymers. Weiterhin betrifft die Erfindung einen entsprechenden Farb-Masterbatch. Derartige Farb-Masterbatches finden Verwendung bei der Einfärbung von Polymerwerkstoffen.The present invention relates to a process for the preparation of a color masterbatch based on a thermoplastic silicone copolymer. Furthermore, the invention relates to a corresponding color masterbatch. Such color masterbatches are used in the coloring of polymer materials.

Farb-Masterbatches werden derzeit typischerweise aus Kunststoffgranulaten und Farbmitteln hergestellt. Hierfür hat sich am Markt ein eigener Industriezweig gebildet, der sich darauf spezialisiert hat. Die Colorierung erfolgt durch Misch- und Schmelzprozess von Farbmittel und Kunststoffgranulat unter Beimischung geringer Mengen von Additiven im Doppelschneckenextruder. Praktiziert wird sowohl die einstufige als auch die zweistufige Masterbatchherstellung. Während bei der einstufigen Fertigung sofort alle Rohstoffkomponenten vorgelegt und extrudiert werden, führt die zweistufige Fertigung über sog. "Monokonzentrate", die im zweiten Schritt nochmals gemischt, und gegebenenfalls mit Additiven versehen und extrudiert werden. Die Homogenität des Farbtons im Kunststoff hängt davon ab, welches Fließverhalten in der Schmelze erreicht wird bzw. wie gut sich der Masterbatch in der Matrix verteilt. Für jede Kunststoffklasse gibt es daher spezielle Masterbatchtypen.Color masterbatches are currently typically made from plastic granules and colorants. For this purpose, a separate industry has been formed on the market, which has specialized in it. The coloration is carried out by mixing and melting of colorant and plastic granules with the addition of small amounts of additives in twin-screw extruder. Both single-stage and two-stage masterbatch production are practiced. While In the single-stage production, all raw material components are initially charged and extruded, the two-stage production leads to so-called "mono-concentrates", which are mixed again in the second step and optionally provided with additives and extruded. The homogeneity of the hue in the plastic depends on which flow behavior is achieved in the melt or how well the masterbatch spreads in the matrix. There are therefore special types of masterbatches for every plastic class.

Eine prinzipielle Problematik der Masterbatchherstellung ist, dass Pigmente, deren Primärpartikel im Größenbereich von wenigen Nanometern bis einigen Mikrometern liegen, in die makromolekularen Werkstoffe im Schmelzemischverfahren eingearbeitet werden müssen. Das Aufschließen der Pigmentaggregate und -agglomerate und das homogene Verteilen der Pigmente in der z.T. sehr hochviskosen Kunststoffschmelze können aber durchaus problematisch sein. Zudem muss ein bereits aufgeschmolzener und granulierter Polymerwerkstoff bei diesem Schmelzecompoundieren erneut aufgeschmolzen und granuliert werden. Dies abhängig vom Verfahren sogar bis zu zweimal. Neben einem hohen energetischen Aufwand, der damit verbunden ist, kann die wiederholte thermische Belastung auch zu einer Schädigung des Masterbatch-Trägermaterials führen in Folge von Kettenabbaureaktionen mit daraus resultierendem Molmassenabbau.A principal problem of masterbatch production is that pigments whose primary particles are in the size range of a few nanometers to a few micrometers must be incorporated into the macromolecular materials in the melt-mixing process. The digestion of the pigment aggregates and agglomerates and the homogeneous distribution of the pigments in the z.T. very high-viscosity plastic melt can be quite problematic. In addition, an already melted and granulated polymer material must be remelted during this melt compounding and granulated. This depends on the procedure even up to twice. In addition to a high energy expenditure, which is associated with it, the repeated thermal stress can also lead to damage of the masterbatch support material as a result of chain degradation reactions resulting in molecular weight degradation.

Das Mischverhalten von Farbmitteln in den jeweiligen Kunststoffen ist - vor allem bei höheren Konzentrationen an Pigmenten bzw. Farbstoffen - nicht vorhersehbar, so dass vor allem die Herstellung von Masterbatches oftmals Schwierigkeiten bereitet, da die in einen jeweiligen Kunststoff einzuarbeitenden Farbmittel, also z.B. Pigmente oder Farbstoffe, oftmals verklumpen oder agglomerieren, so dass starke Inhomogenitäten auftreten. Dies führt zu nachteiligen Eigenschaften des Masterbatches, z.B. was rheologische oder mechanische Eigenschaften anbelangt.The mixing behavior of colorants in the respective plastics is - especially at higher concentrations of pigments or dyes - unpredictable, so that in particular the production of masterbatches often causes difficulties, since the to be incorporated into a particular plastic colorant, For example, pigments or dyes, often clump or agglomerate, so that strong inhomogeneities occur. This leads to disadvantageous properties of the masterbatch, for example as far as rheological or mechanical properties are concerned.

Ein besonders interessanter Kunststoff, der durch seine vorteilhaften Materialeigenschaften ein breites Anwendungsgebiet abdeckt, ist ein Organopolysiloxan/Polyharnstoff/Polyurethan-Blockcopolymer, das in der EP 1 489 129 A1 offenbart ist. Allerdings waren bisher alle Versuche, in dieses Blockcopolymer Farbmittel, vor allem in höheren Konzentrationen einzuarbeiten, erfolglos.A particularly interesting plastic, which covers a wide field of application due to its advantageous material properties, is an organopolysiloxane / polyurea / polyurethane block copolymer, which is described in US Pat EP 1 489 129 A1 is disclosed. However, all attempts to incorporate dye into this block copolymer, especially in higher concentrations, have so far been unsuccessful.

Ausgehend hiervon war es Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung eines Farb-Masterbatches sowie einen entsprechenden Farb-Masterbatch bereitzustellen, wobei sich die Verfahrensführung durch hohe Effizienz und der Farb-Masterbatch durch hohe Kompatibilität gegenüber zugesetzten Farbmitteln und deren eingesetzten Mengen auszeichnen soll.Proceeding from this, it was an object of the present invention to provide a process for the preparation of a color masterbatch and a corresponding color masterbatch, the process being characterized by high efficiency and the color masterbatch by high compatibility with added colorants and their amounts used.

Bezüglich des Verfahrens wird diese Aufgabe mit den Merkmalen des Anspruchs 1, bezüglich des Masterbatches mit den Merkmalen des Anspruchs 11 gelöst. In Anspruch 14 werden mit dem Farb-Masterbatch gefärbte Polymerwerkstoffe bereitgestellt. Die jeweiligen abhängigen Ansprüche stellen dabei vorteilhafte Weiterbildungen der Erfindung dar. Anspruch 17 nennt eine erfindungsgemäße Verwendung.With regard to the method, this object is achieved with the features of claim 1, with respect to the masterbatch having the features of claim 11. Claim 14 provides colored polymer materials with the color masterbatch. The respective dependent claims represent advantageous developments of the invention. Claim 17 mentions a use according to the invention.

Erfindungsgemäß wird ein Verfahren zur Herstellung eines Farb-Masterbatches mit folgenden Schritten bereitgestellt:

  1. a) Mischen mindestens einer mit einer Amino-, Hydroxy- oder Carboxy-Gruppe terminierten Siloxanstruktur der allgemeinen Formel I (Komponente A) :
    Figure imgb0001
     mit
    • R1 unabhängig voneinander ein einwertiger gegebenenfalls durch Fluor oder Chlor substituierter Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen,
    • R2 unabhängig voneinander ein Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O-ersetzt sein können oder einen Arylenrest mit 6 bis 22 Kohlenstoffatomen, besonders bevorzugt -(CH2)3-,
    • X und Y unabhängig voneinander eine Hydroxy-, Carboxy- oder Amino-Gruppe -NR'- mit R' = Wasserstoff, Alkylrest mit 1 bis 10 Kohlenstoffatomen oder Arylrest mit 6 bis 22 Kohlenstoffatomen, besonders bevorzugt -NH2 und n eine Zahl von 1 bis 10000,
      mit mindestens einer bifunktionellen Verbindung (Komponente B), die zwei, mit X und Y durch Polyaddition oder Polykondensation verknüpfbare Gruppen aufweist,
      • b) Polymerbildung der Mischung der Komponenten A und B sowie
      • c) Aufschmelzen des Polymerisats im Extruder oder diskontinuierlichen Innenmischer mit anschließender Granulation.
        Dabei wird vor Abschluss der Polymerbildung, d.h. vor oder während Schritt b), mindestens ein Farbmittel zugesetzt.
According to the invention, a process for the preparation of a color masterbatch is provided with the following steps:
  1. a) mixing at least one amino, hydroxy or carboxy-terminated siloxane structure of the general formula I (component A):
    Figure imgb0001
     With
    • R 1 is independently a monovalent hydrocarbon or fluorine radical having 1 to 20 carbon atoms optionally substituted by fluorine or chlorine,
    • R 2 independently of one another, an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O- or an arylene radical having 6 to 22 carbon atoms, more preferably - (CH 2 ) 3 -,
    • X and Y independently of one another are a hydroxyl, carboxy or amino group -NR'- where R '= hydrogen, alkyl radical having 1 to 10 carbon atoms or aryl radical having 6 to 22 carbon atoms, particularly preferably -NH 2 and n is a number of 1 up to 10000,
      with at least one bifunctional compound (component B) which has two groups which can be linked to X and Y by polyaddition or polycondensation,
      • b) polymer formation of the mixture of components A and B as well
      • c) melting the polymer in the extruder or discontinuous internal mixer with subsequent Granulation.
        In this case, at least one colorant is added before completion of the polymer formation, ie before or during step b).

Die Polymerbildung in Schritt b) erfolgt bevorzugt bei Temperaturen von mindestens 20 °C. Grundsätzlich kann aber auch bei niedrigen Temperaturen gearbeitet werden.The polymer formation in step b) is preferably carried out at temperatures of at least 20 ° C. In principle, however, it is also possible to work at low temperatures.

Die Einmischung der Farbmittel kann erfindungsgemäß in die flüssigen Vorstufen der Siloxan-Copolymere erfolgen. Die homogene Dispergierung von großen Konzentrationen an Farbmitteln in diese relativ niedrigviskosen Systeme ist gut handhabbar und mittels der in der Farben- und Lack-Industrie etablierten Techniken problemlos realisierbar. Die Problematik des Einmischens der Farbmittel in die flüssigen Vorstufen der Polysiloxan-Copolymere ist dabei aber keineswegs als trivial abzutun. Normalerweise werden Polymerwerkstoffe aus Monomeren mit sehr geringen Molmassen aufgebaut. Diese Monomere sind entweder gasförmig, oder flüssig, mit sehr geringen Viskositäten. Die Farbmitteleinarbeitung in polymere Vorstufen, also in die Monomere, ist für die meisten Polymere also gar nicht möglich bzw. nur mit einem sehr großen technischen Aufwand zu realisieren. Daher wird dieser Weg im Allgemeinen auch nicht in der Masterbatchherstellung bestritten. Der Vorteil der Polysiloxan-Copolymere ist, dass die Grundkomponenten keine Monomere im klassischen Sinne sind, sondern eher Oligomere. Besonders die siliziumorganische Verbindung kann sich mit Molmassen von > 10.000 g/mol auszeichnen. Daher hat man es mit den Grundkomponenten der Polysiloxan-Copolymere mit gut handhabbaren Fluiden zu tun. In dem Arbeitsfeld der Polymersynthese kann daher die Einarbeitung von Farbmitteln in eine fluide Vorstufe schon als Neuerung angesehen werden.The interference of the colorants can be carried out according to the invention in the liquid precursors of the siloxane copolymers. The homogeneous dispersion of large concentrations of colorants in these relatively low-viscosity systems is easy to handle and easily implemented by the techniques established in the paint and coatings industry. The problem of mixing the colorant in the liquid precursors of the polysiloxane copolymers is by no means trivial abzutun. Usually polymer materials are built up from monomers with very low molecular weights. These monomers are either gaseous or liquid, with very low viscosities. The colorant incorporation in polymeric precursors, ie in the monomers, is therefore not possible for most polymers or can only be realized with a very large technical outlay. Therefore, this route is generally not contested in masterbatch production either. The advantage of the polysiloxane copolymers is that the basic components are not monomers in the classical sense, but rather oligomers. In particular, the organosilicon compound can be distinguished by molar masses of> 10,000 g / mol. Therefore, one has it with the basic components of the polysiloxane copolymers to do with easy to handle fluids. In the field of polymer synthesis, therefore, the incorporation of colorants in a fluid precursor may already be considered an innovation.

Auf Basis der fluiden Vorstufen ist es möglich, Pasten mit den Grundfarbtönen zu erzeugen. Diese Pasten können vor der Polymersynthese zum Endfarbton gemischt werden. Durch anschließendes Ausreagieren der Komponenten zum fertigen Farb-Masterbatch erhält man das Produkt in nur einem Extrusionsschritt. Neben reduzierten Produktionskosten ist der wesentliche Vorteil, dass das Trägermaterial des Farb-Masterbatches nur ein einziges Mal vor dem Endeinsatz thermisch belastet wird. Dadurch verringert sich der Einfluss thermischer Abbaureaktionen auf die Matrix.Based on the fluid precursors it is possible to produce pastes with the basic shades. These pastes can be mixed to final shade before polymer synthesis. By subsequently reacting the components to the finished color masterbatch, the product is obtained in only one extrusion step. In addition to reduced production costs, the major advantage is that the carrier material of the color masterbatch is only subjected to thermal stress once before the end use. This reduces the influence of thermal degradation reactions on the matrix.

Ein weiterer Vorteil des erfindungsgemäßen Verfahrens ist, dass nach der Dispergierung der Farbmittel in die fluide Polymervorstufe eine weitere Dispergierung und Homogenisierung der Farbmittel in der ausreagierten Polymermatrix im Extruder erfolgt. Dadurch wird die Farbmittelverteilung im Farb-Masterbatch zusätzlich verbessert.A further advantage of the process according to the invention is that, after the dispersion of the colorants into the fluid polymer precursor, there is a further dispersion and homogenization of the colorants in the reacted polymer matrix in the extruder. This additionally improves the colorant distribution in the color masterbatch.

Als Farbmittel werden bevorzugt Pigmente, Farbstoffe oder Mischungen hiervon eingesetzt.The colorants used are preferably pigments, dyes or mixtures thereof.

Als Pigmente kommen sowohl anorganische als auch organische Pigmente in Frage. Zu den anorganischen Pigmenten gehören solche der Gruppe der Oxide, z.B. Eisenoxid (braun, rot, schwarz), Chromoxid (grün), Titandioxid, oder Kohlenstoff, z.B. Ruß-schwarz, oder Chromate, z.B. Bleichromat-gelb, Molybdatorange, oder Komplexe anorganischer Buntpigmente, z.B. Chromtitangelb, Chromeisenbraun, Kobaltblau, Nickeltitangelb, Zinkeisenbraun, Wismutvanadatgelb, oder Sulfide, z.B. Cadmiumsulfid (gelb, orange, rot), Cersulfid (gelb, orange, rot), Ultramarin (violett, blau), Zinksulfid (weiß). Zu den organischen Pigmenten zählen Azopigmente, z.B. verlackte Azopigmente (gelb, rot), Disazopigmente (gelb, orange, rot), Disazokondensationspigmente (gelb, rot), Benzimidazolpigmente (gelb, orange), Metallkomplexpigmente (gelb), Insoindolinpigmente (gelb), Insoindolinonpigmente (gelb), oder auch polyzyklische Pigmente, z.B. Chinacridon (violett, blau), Chinophthalon (gelb), Diketo-Pyrrolo-Pyrrol (orange, rot, violett), Disoxazinpigmente (violett), Indanthron (blau), Perylen (rot, violet), Phthalocyanin (blau, grün).Suitable pigments are both inorganic and organic pigments. The inorganic pigments include those of the group of oxides, for example iron oxide (brown, red, black), chromium oxide (green), titanium dioxide, or carbon, for example carbon black, or chromates, for example lead chromate, molybdate orange, or complexes of inorganic colored pigments , eg chrome titanium yellow, chrome iron brown, cobalt blue, nickel titanium yellow, Zinc iron brown, bismuth vanadate yellow, or sulfides, eg cadmium sulfide (yellow, orange, red), cerium sulphide (yellow, orange, red), ultramarine (purple, blue), zinc sulphide (white). The organic pigments include azo pigments, eg laked azo pigments (yellow, red), disazo pigments (yellow, orange, red), disazo condensation pigments (yellow, red), benzimidazole pigments (yellow, orange), metal complex pigments (yellow), insoindoline pigments (yellow), insoindolinone pigments (yellow), or also polycyclic pigments, eg quinacridone (violet, blue), quinophthalone (yellow), diketo-pyrrolo-pyrrole (orange, red, violet), disoxazine pigments (violet), indanthrone (blue), perylene (red, violet ), Phthalocyanine (blue, green).

Als Farbstoffe kommen sowohl lösliche Farbstoffe, z.B. Anthrachinon, Chinophthalon, Pyrazolon, Perinon und Monoazofarbstoffe, als auch fluoreszierende Farbstoffe, z.B. Perylen, Naphthalimid, Cuminderivate, Thioindigo, Thioxanthen-Benzanthron in Frage.Dyes include both soluble dyes, e.g. Anthraquinone, quinophthalone, pyrazolone, perinone and monoazo dyes, as well as fluorescent dyes, e.g. Perylene, naphthalimide, cumin derivatives, thioindigo, thioxanthene benzanthrone in question.

Erfindungsgemäß wird ebenso ein Farb-Masterbatch bereitgestellt, der nach dem zuvor beschriebenen Verfahren herstellbar ist.The invention likewise provides a color masterbatch which can be produced by the method described above.

Überraschenderweise hat sich gezeigt, dass der erfindungsgemäße Farb-Masterbatch, der sich nach der erfindungsgemäßen Verfahrensführung herstellen lässt, eine ausgezeichnete Homogenität, d. h. keinen Konzentrationsgradienten des Farbmittels im Masterbatch, aufweist. Als weitere vorteilhafte Eigenschaften des Farb-Masterbatches sind die hohe Zugfestigkeit, die hohe thermische Beständigkeit, ein ausgezeichnetes Spannungs-Dehnungs-Verhalten oder rheologisches Verhalten sowie ein ausgezeichnetes Permeationsverhalten für eine Vielzahl von Stoffen zu nennen. Weiterhin erweist sich der Farb-Masterbatch sehr tolerant gegenüber einer Vielzahl von Kunststoffen, mit denen in für die Kunststoffverarbeitung und -modifizierung üblichen Einsatzkonzentrationen eine gute Verträglichkeit besteht.Surprisingly, it has been found that the color masterbatch according to the invention, which can be prepared by the method according to the invention, exhibits excellent homogeneity, ie no concentration gradient of the colorant in the masterbatch. Further advantageous properties of the color masterbatch include high tensile strength, high thermal stability, excellent stress-strain behavior or rheological behavior, and excellent permeation behavior for a large number of substances. Farther the color masterbatch proves to be very tolerant of a large number of plastics with which good compatibility is possible in the usual concentrations for plastics processing and modification.

Ein entscheidender Vorteil des Farb-Masterbatches in Verbindung mit anderen Kunststoffen ist das bessere Fließverhalten der Matrix in der Schmelze, wodurch gerade komplizierte Spritzgussteile eine bessere und schnellere Spritzformbeladung erfahren und damit eine höhere Wirtschaftlichkeit gegeben ist. Ein weiterer wichtiger Vorteil des Farb-Masterbatches ist es, dass bei Extrusionsanwendungen eine enorme Durchsatzsteigerung erzielt werden kann.A decisive advantage of the color masterbatch in connection with other plastics is the better flow behavior of the matrix in the melt, whereby particularly complicated injection molded parts experience a better and faster injection mold loading and thus a higher economic efficiency is given. Another important advantage of the color masterbatch is that it can achieve an enormous increase in throughput in extrusion applications.

Die erfindungsgemäß eingesetzten Polysiloxan-Copolymere bestehen, wie bereits beschrieben aus zwei bzw. drei Komponenten, aus der Siloxanstruktur A und den organischen Komponenten B und gegebenenfalls C. Generell handelt es sich bei diesen Copolymeren um alternierende Blockcopolymere vom Typ AB (bestehend aus mindestens zwei Blocksequenzen) oder vom Typ ABA (bestehend aus drei Blöcken). Gebildet werden diese Polymere entweder durch Polyadditionsreaktion oder Polykondensationsreaktion unter Abspaltung von z.B. Wasser. Für die Bildung dieser Polymere sind im Allgemeinen zwei bifunktionelle Komponenten erforderlich. Zum einen eine bifunktionelle Komponente A, welche eine organische Siliciumverbindung enthält und zum anderen eine bifunktionelle Komponente B. Die funktionellen Gruppen der Komponente B müssen dabei derart beschaffen sein, dass sie in der Lage sind, mit den funktionellen Gruppen der Komponente A reagieren zu können. Werden Komponente A und Komponente B in stöchiometrischen Verhältnissen, d.h. im molaren Verhältnis 1:1 eingesetzt, bilden sich unter bestimmten Reaktionsbedingungen und gegebenenfalls unter Zugabe eines Katalysators lange Makromoleküle, in denen sich Komponente A und Komponente B abwechseln.The polysiloxane copolymers used according to the invention consist, as already described, of two or three components of the siloxane structure A and the organic components B and optionally C. These copolymers are generally of the type AB alternating block copolymers (consisting of at least two block sequences ) or type ABA (consisting of three blocks). These polymers are formed either by polyaddition reaction or polycondensation reaction with elimination of eg water. For the formation of these polymers, two bifunctional components are generally required. On the one hand, a bifunctional component A, which contains an organic silicon compound and, on the other hand, a bifunctional component B. The functional groups of component B must be such that they are able to react with the functional groups of component A. Are component A and component B in stoichiometric ratios, ie in the molar Used ratio 1: 1, formed under certain reaction conditions and optionally with the addition of a catalyst long macromolecules in which component A and component B alternate.

In speziellen Fällen wird in diese Polysiloxan-Copolymere eine dritte Komponente C eingebaut, die auch als Ketten-extender bezeichnet wird. Die Reaktion zum Makromolekül erfolgt in der Regel in zwei Stufen, wobei auch das Einstufenverfahren möglich ist. Zuerst werden wieder Komponente A und Komponente B zur Reaktion gebracht. Allerdings ist das stöchiometrische Verhältnis von A und B so gewählt, dass nur definierte kurze Moleküle mit der exakten Struktur BAB entstehen. Das molare Verhältnis von A zu B beträgt hier 1:2. In einem zweiten, zeitlich nachgelagerten Reaktionsschritt erfolgt dann die Zugabe der Komponente C. Komponente C ist ebenfalls bifunktionell und die funktionellen Gruppen von Komponente C sind in der Lage, mit den funktionellen Gruppen von Komponente B zu reagieren. Bei Reaktion von Komponente C und Komponente B entstehen dann wiederum Makromoleküle mit der Struktur .....BABCBABC.....In special cases, a third component C, which is also referred to as a chain extender, is incorporated in these polysiloxane copolymers. The reaction to the macromolecule is usually carried out in two stages, wherein the one-step process is possible. First, component A and component B are reacted again. However, the stoichiometric ratio of A and B is chosen so that only defined short molecules with the exact structure BAB are formed. The molar ratio of A to B here is 1: 2. Component C is also bifunctional and the functional groups of component C are capable of reacting with the functional groups of component B. In a second, later reaction step, the addition of the component C. Upon reaction of component C and component B, macromolecules with the structure ..... BABCBABC .....

Die Siloxanstruktur A ist im Copolymer stark unpolar. Die organischen Komponeten B und C dagegen bringen in das Copolymer polare Gruppen ein. Durch die Variation von unpolaren und polaren Blöcken können die Polysiloxan-Copolymere an verschiedenste Polymerwerkstoffe bezüglich der Verträglichkeit angepasst werden. Die Folge ist, dass aus einem bzw. nur wenigen Basiswerkstoffen Farb-Masterbatches für nahezu alle Polymerwerkstoffe erzeugt werden können. Man kann auf Basis von Polysiloxan-Copolymeren also Universal-Masterbatches für nahezu alle Polymerwerkstoffe, zumindest jedoch jeweils große Polymerwerkstoffgruppen, wie Polyolefine, Polyester, Styrol-basierte Polymere etc. erzeugen.The siloxane structure A is highly non-polar in the copolymer. On the other hand, the organic components B and C introduce polar groups into the copolymer. By varying nonpolar and polar blocks, the polysiloxane copolymers can be adapted to a wide variety of polymer materials in terms of compatibility. The result is that one or only a few basic materials can be used to produce color masterbatches for almost all polymer materials. On the basis of polysiloxane copolymers, it is thus possible to use universal masterbatches for virtually all polymer materials, but at least large polymer material groups in each case, such as polyolefins, polyesters, styrene-based polymers, etc.

Neben der universellen Einsetzbarkeit ist ein weiterer Vorteil des Farb-Masterbatches, dass das Polymer nicht nur eingefärbt wird, sondern dass das Farb-Masterbatch-Trägermaterial, also das Polysiloxan-Copolymer, gleichzeitig als Prozesshilfsmittel wirkt. Durch Zugabe des Farb-Masterbatches können bei sonst konstanten Prozessparametern im Spritzgussprozess deutlich die Zykluszeiten gesenkt werden. Im Extrusionsverfahren kann der Durchsatz bei sonst konstanten Bedingungen signifikant gesteigert werden. Das bedeutet in allen Fällen eine Verbesserung der Wirtschaftlichkeit des Verfahrens.In addition to the universal applicability is a further advantage of the color masterbatch that the polymer is not only dyed, but that the color masterbatch support material, ie the polysiloxane copolymer, simultaneously acts as a processing aid. By adding the color masterbatch, the cycle times can be significantly reduced while the process parameters in the injection molding process are otherwise constant. In the extrusion process, the throughput can be increased significantly under otherwise constant conditions. This means in all cases an improvement in the economics of the process.

Da Polysiloxan-Copolymere zu den thermoplastischen Elastomeren gehören, können diese Werkstoffe in speziellen Fällen als Zähigkeitsmodifikatoren für andere thermoplastische Werkstoffe wirken. Man kann neben dem Einfärben und verbesserter Verarbeitbarkeit also auch weitere Effekte, wie Zähigkeitsmodifikation mittels dieses Farb-Masterbatches erreichen.Since polysiloxane copolymers are among the thermoplastic elastomers, these materials can act as toughening modifiers for other thermoplastic materials in special cases. In addition to dyeing and improved processability, it is thus also possible to achieve further effects, such as toughness modification, by means of this color masterbatch.

Die Siloxanstruktur ist unpolar. Bei dem Mischen/Verblenden der Polysiloxan-Copolymere mit anderen Polymerwerkstoffen lagern sich die Siloxan-Sequenzen der Copolymere an die Oberfläche der modifizierten Polymerwerkstoffe. Das Ergebnis ist, dass besonders polare Werkstoffe, wie PET oder PA, an der Oberfläche polar abgeschirmt, also unpolar gemacht werden. Das Ergebnis ist, dass Oberflächen stark wasserabweisend ausgerüstet werden können.The siloxane structure is non-polar. In blending / blending the polysiloxane copolymers with other polymeric materials, the siloxane sequences of the copolymers attach to the surface of the modified polymeric materials. The result is that particularly polar materials, such as PET or PA, are polar shielded on the surface, that is, they are made non-polar. The result is that surfaces can be highly water-repellent equipped.

Ebenso konnte gezeigt werden, dass die Elastizität von Polymerwerkstoffen selbst bei niedrigen Temperaturen verbessert wird und damit neue Einsatzmöglichkeiten eröffnet werden. Mit der vorgeschlagenen Dispergierung der Pigmente in das Copolymer kann eine fest-flüssig-Dispergierung vorgenommen und z.B. durch Mühlen ein optimaler Aufschluss der Pigmente erfolgen. Dadurch ist Homogenität, Flexibilität für die Endfarbtonformulierung durch Einsatz von Dosiertechnik und optimale Nutzung des Farbstärkevermögens der Pigmente gewährleistet.It could also be shown that the elasticity of polymer materials even at low temperatures is improved and thus new applications are opened. With the proposed dispersion of the pigments in the copolymer, a solid-liquid dispersion can be carried out and carried out, for example by mills an optimal digestion of the pigments. This ensures homogeneity, flexibility for the final color formulation through the use of dosing technology and optimal use of the color strength of the pigments.

Das Farbmittel kann dabei bevorzugt in die noch nicht polymerisierten Komponenten bzw. die entsprechenden Mischungen hieraus eingemischt werden (vor oder während Schritt a)), als alternativer und/oder zusätzlicher Verfahrensschritt ist es aber auch denkbar, das Farbmittel während der Polymerisierung, d.h. vor deren Abschluss einzumischen (Schritt b)).The colorant may preferably be mixed into the not yet polymerized components or the corresponding mixtures thereof (before or during step a)), but as an alternative and / or additional process step it is also conceivable to use the colorant during the polymerization, i. to meddle before their conclusion (step b)).

Bezüglich der Verfahrensführung hat sich als vorteilhaft herausgestellt, wenn das mindestens eine Farbmittel, bezogen auf das Gewicht des gebildeten Polymers, in einer Menge von 1 bis 80 Gew.-%, bevorzugt 10 bis 50 Gew.-% zugegeben wird. Insbesondere sind die Farbmittel ausgewählt aus der Gruppe bestehend aus Pigmenten und/oder Farbstoffen.With regard to the process procedure, it has proven to be advantageous if the at least one colorant, based on the weight of the polymer formed, in an amount of 1 to 80 wt .-%, preferably 10 to 50 wt .-% is added. In particular, the colorants are selected from the group consisting of pigments and / or dyes.

Vorzugsweise ist die bifunktionale Verbindung ausgewählt aus der Gruppe bestehend aus Diisocyanaten, Diaminen, Diolen, Dicarbonsäuren, Diformaldehydterminierten Verbindungen und Mischungen hiervon.Preferably, the bifunctional compound is selected from the group consisting of diisocyanates, diamines, diols, dicarboxylic acids, formaldehyde-terminated compounds, and mixtures thereof.

Das Diisocyanat weist dabei vorzugsweise die allgemeine Formel II auf,

        O=C=N-R3-N=C=O     (II)

mitThe diisocyanate preferably has the general formula II,

O = C = NR 3 -N = C = O (II)

With

R3 ein gegebenenfalls durch Fluor oder Chlor substituierter Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen.R 3 is an optionally substituted by fluorine or chlorine alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms.

Eine weitere bevorzugte Variante sieht vor, dass unmittelbar nach Schritt a) zu dem Zwischenprodukt der Komponenten A und B mindestens ein Kettenextender (Komponente C) mit der allgemeinen Formel III:

        H-V-R4-W-H     (III)

mit
R4 ein gegebenenfalls durch Fluor, Chlor, C1-C6-Alkyl- oder C1-C6-Alkylester substituierter Alkylenrest mit 1 bis 700 C-Atomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O-, -COO-, -OCO- oder -OCOO- ersetzt sein können, und
V, W unabhängig voneinander -O- oder -NR5-, wobei R5 Wasserstoff, ein Alkylrest mit 1 bis 10 C-Atomen oder ein Arylrest mit 6 bis 22 C-Atomen ist, zugesetzt wird.A further preferred variant provides that immediately after step a) to the intermediate of components A and B at least one chain extender (component C) having the general formula III:

HVR 4 -WH (III)

With
R 4 is an optionally substituted by fluorine, chlorine, C 1 -C 6 alkyl or C 1 -C 6 alkyl ester alkylene radical having 1 to 700 carbon atoms, in which non-adjacent methylene units by groups -O-, -COO- , -OCO- or -OCOO- may be replaced, and
V, W independently of one another -O- or -NR 5 -, wherein R 5 is hydrogen, an alkyl radical having 1 to 10 C atoms or an aryl radical having 6 to 22 carbon atoms, is added.

Als Komponente C sind Diamine und Diole, insbesondere 1,4-Butandiol, 1,6-Hexandiol, Ethylenglykol, 4,4'-Methylen-bis(2-chloranilin), besonders bevorzugt.As component C, diamines and diols, in particular 1,4-butanediol, 1,6-hexanediol, ethylene glycol, 4,4'-methylene-bis (2-chloroaniline), are particularly preferred.

Weiterhin ist die Einmischung weiterer Additive, z.B. ausgewählt aus Nanofüllstoffen, Stabilisatoren, Antistatika, Flammschutzmittel, Haftvermittler, Nukleierungsmittel, Treibmittel, antibakterielle Mittel und Mischungen hiervon, möglich. Die Menge der Additive beträgt dabei bevorzugt zwischen 1 und 80 Gew.-%, bezogen auf das Gewicht des gebildeten Polymers.Furthermore, it is possible to incorporate further additives, for example selected from nanofillers, stabilizers, antistatics, flame retardants, adhesion promoters, nucleating agents, blowing agents, antibacterial agents and mixtures thereof. The amount of additives is preferably between 1 and 80 wt .-%, based on the weight of the polymer formed.

Bei ökonomischer Betrachtung der eingesetzten Reaktanden, ist es verfahrenstechnisch vorteilhaft, wenn die Verbindungen der allgemeinen Formel I und die bifunktionale Verbindung in äquimolaren Verhältnissen eingesetzt werden.In economic consideration of the reactants used, it is procedurally advantageous if the compounds of general formula I and the bifunctional compound are used in equimolar ratios.

Da viele der zuvor aufgezählten Edukte feuchtigkeits- bzw. luftempfindlich sind, ist es vorteilhaft, wenn das Verfahren unter Ausschluss von Feuchtigkeit und unter Schutzgas, z. B. Stickstoff oder Argon, durchgeführt wird.Since many of the previously enumerated educts are sensitive to moisture or air, it is advantageous if the process in the absence of moisture and under inert gas, for. As nitrogen or argon is performed.

Besonders hohe Ausbeuten lassen sich erzielen, wenn beim Verfahren zur Herstellung des Farb-Masterbatches ein Katalysator aus der Gruppe enthaltend Dialkylzinnverbindungen, Dibutylzinndilaurat, Dibutylzinndiacetat, tertiäre Amine, N,N-Dimethylcyclohexanamin, 2-Dimethylaminoethanol, 4-Dimethylaminopyridin und/oder Mischungen hieraus zugesetzt wird.Particularly high yields can be achieved if, in the process for the preparation of the color masterbatch, a catalyst from the group comprising dialkyltin compounds, dibutyltin dilaurate, dibutyltin diacetate, tertiary amines, N, N-dimethylcyclohexanamine, 2-dimethylaminoethanol, 4-dimethylaminopyridine and / or mixtures thereof is added becomes.

Ein bevorzugter Farb-Masterbatch enthält ein Blockcopolymer der allgemeinen Formel IV

Figure imgb0002
mit

  • R1 unabhängig voneinander ein einwertiger gegebenenfalls durch Fluor oder Chlor substituierter Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen,
  • R2 unabhängig voneinander ein Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen,
  • R3 ein gegebenenfalls durch Fluor oder Chlor substituierter Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen
  • B, B': eine reaktive oder nicht reaktive Endgruppe, welche kovalent an das Polymer gebunden ist,
  • n: eine Zahl von 1 bis 10000,
  • a: eine Zahl von mindestens 1,
    sowie mindestens ein Farbmittel.
    Ein weiterer bevorzugter Farb-Masterbatch enthält ein Blockcopolymer der allgemeinen Formel V
    Figure imgb0003
     mit
  • R1 unabhängig voneinander ein einwertiger gegebenenfalls durch Fluor oder Chlor substituierter Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen,
  • R2 unabhängig voneinander ein Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen,
  • R3 ein gegebenenfalls durch Fluor oder Chlor substituierter Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen
  • R4 ein gegebenenfalls durch Fluor, Chlor, C1-C6-Alkyl- oder C1-C6-Alkylester substituierter Alkylenrest mit 1 bis 700 C-Atomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O-, -COO-, -OCO- oder -OCOO- ersetzt sein können, und
  • V, W unabhängig voneinander -O- oder -NR5-, wobei R5 Wasserstoff, ein Alkylrest mit 1 bis 10 C-Atomen oder ein Arylrest mit 6 bis 22 C-Atomen ist,
  • B, B': eine reaktive oder nicht reaktive Endgruppe, welche kovalent an das Polymer gebunden ist,
  • n: eine Zahl von 1 bis 10000,
  • a: eine Zahl von mindestens 1,
    sowie mindestens ein Farbmittel.
A preferred color masterbatch contains a block copolymer of the general formula IV
Figure imgb0002
 With
  • R 1 is independently a monovalent hydrocarbon or fluorine radical having 1 to 20 carbon atoms optionally substituted by fluorine or chlorine,
  • R 2 independently of one another an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms,
  • R 3 is optionally substituted by fluorine or chlorine Alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms
  • B, B ': a reactive or non-reactive end group which is covalently bonded to the polymer,
  • n: a number from 1 to 10,000,
  • a: a number of at least 1,
    and at least one colorant.
    Another preferred color masterbatch contains a block copolymer of the general formula V.
    Figure imgb0003
     With
  • R 1 is independently a monovalent hydrocarbon or fluorine radical having 1 to 20 carbon atoms optionally substituted by fluorine or chlorine,
  • R 2 independently of one another an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms,
  • R 3 is an optionally substituted by fluorine or chlorine alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms
  • R 4 is an optionally substituted by fluorine, chlorine, C 1 -C 6 alkyl or C 1 -C 6 alkyl ester alkylene radical having 1 to 700 carbon atoms, in which non-adjacent methylene units by groups -O-, -COO- , -OCO- or -OCOO- can be replaced, and
  • V, W independently of one another are -O- or -NR 5 -, where R 5 is hydrogen, an alkyl radical having 1 to 10 C atoms or an aryl radical having 6 to 22 C atoms,
  • B, B ': a reactive or non-reactive end group which is covalently bonded to the polymer,
  • n: a number from 1 to 10,000,
  • a: a number of at least 1,
    and at least one colorant.

Weiterhin können weitere Additive, z.B. Nanofüllstoffe, Stabilisatoren, Antistatika, Flammschutzmittel, Haftvermittler, Nukleierungsmittel, Treibmittel, antibakterielle Mittel und Mischungen hiervon enthalten sein. Die Menge der Additive beträgt dabei bevorzugt 1 bis 80 Gew.-%, bezogen auf das Gewicht des gebildeten Polymers.Furthermore, other additives, e.g. Nanofillers, stabilizers, antistatic agents, flame retardants, adhesion promoters, nucleating agents, blowing agents, antibacterial agents and mixtures thereof may be contained. The amount of the additives is preferably 1 to 80 wt .-%, based on the weight of the polymer formed.

Ebenso wird erfindungsgemäß ein eingefärbter Polymerwerkstoff, der den erfindungsgemäßen Farb-Masterbatch enthält, bereitgestellt.Likewise, according to the invention, a colored polymer material containing the color masterbatch according to the invention is provided.

Als vorteilhaft hat sich insbesondere herausgestellt, dass der Farb-Masterbatch eine hohe Verträglichkeit mit einer Vielzahl von Polymerwerkstoffen bzw. Blends hiervon aufweist. Hierzu zählen insbesondere Polyethylen, Polypropylen, Polyamid, Polyethylenterephthalat, Polybutylenterephthalat, thermoplastische Elastomere auf Basis von vernetztem Kautschuk, Ethylen-Vinylacetat, Polyhydroxybutyrat und/oder Copolymere oder Blends hiervon.In particular, it has turned out to be advantageous that the color masterbatch has a high compatibility with a large number of polymer materials or blends thereof. These include in particular polyethylene, polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, thermoplastic elastomers based on crosslinked rubber, ethylene-vinyl acetate, polyhydroxybutyrate and / or copolymers or blends thereof.

Ebenso kann der Farb-Masterbatch auf für Polystyrol, schlagzähmodifiziertes Polystyrol, Styrol-Acrylnitril-Copolymere, Acrylnitril-Butadien-Styrol-Copolymere, Polyvinylchlorid, Polymethylmethacrylat, Polycarbonat, Polyaryletherketon, Polyacrylnitril, Polyetherimid, Polyethylennaphthalat, Polyethersulfon, Polyimid, Polyketon, Polyoxymethylen, Polyphenylensulfid, Polyphenylensulfon, Polysulfon, Styrol-Butadien-Kautschuk, Acrylnitril-Butadien-Kautschuk, Naturkautschuk und deren Copolymere oder Blends eingesetzt werden.Likewise, the color masterbatch may be based on polystyrene, impact-modified polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride, polymethyl methacrylate, polycarbonate, Polyaryletherketone, polyacrylonitrile, polyetherimide, polyethylene naphthalate, polyethersulfone, polyimide, polyketone, polyoxymethylene, polyphenylene sulfide, polyphenylene sulfone, polysulfone, styrene-butadiene rubber, acrylonitrile-butadiene rubber, natural rubber and their copolymers or blends.

Die Polymerwerkstoffe sind dabei insbesondere herstellbar durch Mischen mindestens eines Polymerwerkstoffs mit dem Farb-Masterbatch in geschmolzenem Zustand und Abkühlen der Mischung.The polymer materials are in particular produced by mixing at least one polymer material with the color masterbatch in the molten state and cooling the mixture.

Bevorzugt liegen die Polymerwerkstoffe in Form eines Formkörpers erhältlich durch einen formgebenden Prozess, ausgewählt aus der Gruppe bestehend aus Spritzgießen, Extrudieren, Formpressen, Walzenrotation, Rotationsformen, Lasersintern, Fused Deposition Modelling (FDM), Granulieren und/oder Gießen vor.Preferably, the polymeric materials are in the form of a molded article obtainable by a molding process selected from the group consisting of injection molding, extrusion, compression molding, roll rotation, rotational molding, laser sintering, fused deposition modeling (FDM), granulation and / or casting.

Die vorliegende Erfindung wird anhand der nachfolgenden, beispielhaft gehaltenen Ausführungen näher erläutert, ohne die Erfindung auf die dort dargestellten Parameter beschränken zu wollen.The present invention will be explained in more detail with reference to the following exemplary embodiments, without wishing to restrict the invention to the parameters presented there.

Alle im Folgenden beschriebenen Versuche wurden diskontinuierlich mit einem Laborkneter der Firma Brabender (Kammervolumen ca. 50cm3) durchgeführt. Die Geschwindigkeit der Knetelemente betrug für alle Versuche 60U/min. Die Herstellung der Farb-Masterbatches erfolgte jeweils aus einer Polyadditionsreaktion von Aminopropyl-terminierten Polydimethylsiloxan (atPDMS) mit einem mittleren Molekulargewicht von 2700g/mol und Tetramethylxylen Diisocyanat (TMXDI) sowie der Zugabe von Farbpigmenten.All experiments described below were carried out discontinuously with a laboratory kneader from Brabender (chamber volume about 50 cm 3 ). The speed of the kneading elements was 60 rpm for all experiments. The color masterbatches were each prepared from a polyaddition reaction of aminopropyl-terminated polydimethylsiloxane (atPDMS) having an average molecular weight of 2700 g / mol and tetramethylxylene diisocyanate (TMXDI) and the addition of color pigments.

Beispiel 1:Example 1:

Zur Herstellung eines Farb-Masterbatches wurden 40 g des atPDMS in den auf 70 °C vortemperierten mit 60 U/min laufenden Laborkneter gegeben. Anschließend wurden 18,7 g (das entspricht 30 Gew.-% auf die Gesamtrezeptur) des anorganischen Pigmentes TiO2 hinzugegeben und über einen Zeitraum von 300 s isotherm mit dem fluiden atPDMS gemischt. Im folgenden Arbeitsschritt wurden 3,6 g des TMXDI hinzudosiert. Nach 120 s isothermer Reaktionszeit wurde der Kneter mit 20 K/min auf 180 °C geheizt. Während des Heizens reagierten das atPDMS und das TMXDI in Anwesenheit des anorganischen Pigmentes vollständig zu einem Polysiloxan-Harnstoff-Copolymer aus. Bei 180 °C befand sich die gebildete Farb-Masterbatchmatrix im Schmelzezustand. Nach Erreichen der Temperatur von 180 °C wurde das System für weitere 180 s in der Schmelze gemischt und somit homogenisiert, anschließend dem Laborkneter entnommen und auf Raumtemperatur abgekühlt.To produce a color masterbatch, 40 g of the atPDMS were added to the laboratory kneader, which was preheated to 70 ° C. and running at 60 rpm. Subsequently, 18.7 g (corresponding to 30% by weight of the total formulation) of the inorganic pigment TiO 2 were added and mixed isothermally with the fluid atPDMS over a period of 300 s. In the following step, 3.6 g of the TMXDI were added. After 120 s isothermal reaction time, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the inorganic pigment. At 180 ° C, the color masterbatch matrix formed was in the melt state. After reaching the temperature of 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.

Beispiel 2:Example 2:

Zur Herstellung eines Farb-Masterbatches wurden 40 g des atPDMS in den auf 70 °C vortemperierten mit 60 U/min laufenden Laborkneter gegeben. Anschließend wurden 18,7 g (das entspricht 30 Gew.-% auf die Gesamtrezeptur) des organischen Pigmentes Phthalocyanin Grün Pigment hinzugegeben und über einen Zeitraum von 300 s isotherm mit dem fluiden atPDMS gemischt. Im folgenden Arbeitsschritt wurden 3,6 g des TMXDI hinzudosiert. Nach 120 s Reaktionsdauer bei konstanter Temperatur wurde der Kneter mit 20 K/min auf 180 °C geheizt. Während des Heizens reagierten das atPDMS und das TMXDI vollständig zu einem Polysiloxan-Harnstoff-Copolymer aus. Bei 180 °C befand sich die gebildete Farb-Masterbatchmatrix im Schmelzezustand. Nach Erreichen der 180 °C wurde das System für weitere 180 s in der Schmelze gemischt und somit homogenisiert, anschließend dem Laborkneter entnommen und auf Raumtemperatur abgekühlt.To produce a color masterbatch, 40 g of the atPDMS were added to the laboratory kneader, which was preheated to 70 ° C. and running at 60 rpm. Subsequently, 18.7 g (corresponding to 30% by weight of the total formulation) of the organic pigment phthalocyanine green pigment were added and mixed isothermally with the fluid atPDMS over a period of 300 s. In the following step, 3.6 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer out. At 180 ° C, the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.

Beispiel 3:Example 3:

Zur Herstellung eines Farb-Masterbatches wurden 40 g des atPDMS in den auf 70 °C vortemperierten mit 60 U/min laufenden Laborkneter gegeben. Anschließend wurden 43,6 g (das entspricht 50 Gew.-% auf die Gesamtrezeptur) des anorganischen Pigmentes TiO2 hinzugegeben und über einen Zeitraum von 300 s isotherm mit dem fluiden atPDMS gemischt. Im folgenden Arbeitsschritt wurden 3,6 g des TMXDI hinzudosiert. Nach 120 s Reaktionsdauer bei konstanter Temperatur wurde der Kneter mit 20 K/min auf 180 °C geheizt. Während des Heizens reagierten das atPDMS und das TMXDI vollständig zu einem Polysiloxan-Harnstoff-Copolymer aus. Bei 180 °C befand sich die gebildete Farb-Masterbatchmatrix im Schmelzezustand. Nach Erreichen der 180 °C wurde das System für weitere 180 s in der Schmelze gemischt und somit homogenisiert, anschließend dem Laborkneter entnommen und auf Raumtemperatur abgekühlt.To produce a color masterbatch, 40 g of the atPDMS were added to the laboratory kneader, which was preheated to 70 ° C. and running at 60 rpm. Subsequently, 43.6 g (corresponding to 50% by weight of the total formulation) of the inorganic pigment TiO 2 were added and mixed isothermally with the fluid atPDMS over a period of 300 s. In the following step, 3.6 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer. At 180 ° C, the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.

Beispiel 4:Example 4:

Vorbereitend zur Farb-Masterbatch-Herstellung wurden 3,6 g des TMXDI mit 18,7 g des anorganischen Pigmentes TiO2 zu einer Paste gemischt. Die Herstellung des Farb-Masterbatches erfolgte durch Dosierung von 40 g des atPDMS in den auf 70 °C vortemperierten und mit 60 U/min laufenden Laborkneter. Anschließend wurde die im ersten Schritt erzeugte Paste hinzugegeben. Nach 240 s isothermer Reaktionszeit wurde der Kneter mit 20 K/min auf 180 °C geheizt. Während des Heizens reagierten das atPDMS und das TMXDI vollständig zu einem Polysiloxan-.Harnstoff-Copolymer aus. Bei 180 °C befand sich die gebildete Farb-Masterbatchmatrix im Schmelzezustand. Nach Erreichen der 180 °C wurde das System für weitere 180 s in der Schmelze gemischt und somit homogenisiert, anschließend dem Laborkneter entnommen und auf Raumtemperatur abgekühlt.Preparing for the color masterbatch preparation, 3.6 g of the TMXDI were mixed with 18.7 g of the inorganic pigment TiO 2 to form a paste. The color masterbatch was prepared by metering 40 g of the atPDMS into the laboratory kneader preheated to 70 ° C. and running at 60 rpm. Subsequently was added the paste produced in the first step. After 240 s isothermal reaction time, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer. At 180 ° C, the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and thus homogenized, then removed from the laboratory kneader and cooled to room temperature.

Beispiel 5:Example 5:

Vorbereitend zur Farb-Masterbatch-Herstellung wurden 50 Gew.-% eines anorganischen Kobalt-Pigmentes auf einem Reibstuhl in das fluide atPDMS homogen eingearbeitet. Zur Herstellung eines Farb-Masterbatches wurden 70 g der Paste in den auf 70 °C vortemperierten mit 60 U/min laufenden Laborkneter gegeben. Anschließend wurden 3,2 g des TMXDI hinzudosiert. Nach 120 s Reaktionsdauer bei konstanter Temperatur wurde der Kneter mit 20 K/min auf 180 °C geheizt. Während des Heizens reagierten das atPDMS und das TMXDI in Anwesenheit des Farbmittels vollständig zu einem Polysiloxan-Harnstoff-Copolymer aus. Bei 180 °C befand sich die gebildete Farb-Masterbatchmatrix im Schmelzezustand. Nach Erreichen der 180 °C wurde das System für weitere 180 s in der Schmelze gemischt und anschließend dem Laborkneter entnommen und auf Raumtemperatur abgekühlt. Durch nachfolgendes Granulieren wurde ein rieselfähiges, klebfreies Farb-Masterbatch erhalten.Preparing for the color masterbatch preparation, 50% by weight of an inorganic cobalt pigment was homogeneously incorporated in a friction mill into the fluid atPDMS. To prepare a color masterbatch, 70 g of the paste were placed in the laboratory kneader running at 70 ° C. at 60 rpm. Subsequently, 3.2 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the colorant. At 180 ° C, the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and then removed from the laboratory kneader and cooled to room temperature. Subsequent granulation gave a free-flowing, tack-free color masterbatch.

Beispiel 6:Example 6:

Vorbereitend zur Farb-Masterbatch-Herstellung wurden 40 Gew.-% eines organischen Gelb-Pigmentes auf einem Reibstuhl in das fluide atPDMS homogen eingearbeitet. Zur Herstellung eines Farb-Masterbatches wurden 55 g der Paste in den auf 70 °C vortemperierten mit 60 U/min laufenden Laborkneter gegeben. Anschließend wurden 2,6 g des TMXDI hinzudosiert. Nach 120 s Reaktionsdauer bei konstanter Temperatur wurde der Kneter mit 20 K/min auf 180 °C geheizt. Während des Heizens reagierten das atPDMS und das TMXDI in Anwesenheit des Farbmittels vollständig zu einem Polysiloxan-Harnstoff-Copolymer aus. Bei 180 °C befand sich die gebildete Farb-Masterbatchmatrix im Schmelzezustand. Nach Erreichen der 180 °C wurde das System für weitere 180 s in der Schmelze gemischt und anschließend dem Laborkneter entnommen und auf Raumtemperatur abgekühlt. Durch nachfolgendes Granulieren wurde ein rieselfähiges, klebfreies Farb-Masterbatch erhalten.Preparing for the color masterbatch preparation were 40 wt .-% of an organic yellow pigment on a Grinding wheel homogeneously incorporated into the fluid atPDMS. To prepare a color masterbatch, 55 g of the paste were placed in the laboratory kneader running at 70 ° C. at 60 rpm. Subsequently, 2.6 g of the TMXDI were added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the atPDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the colorant. At 180 ° C, the color masterbatch matrix formed was in the melt state. After reaching 180 ° C, the system was mixed for a further 180 s in the melt and then removed from the laboratory kneader and cooled to room temperature. Subsequent granulation gave a free-flowing, tack-free color masterbatch.

Beispiele 7-9:Examples 7-9:

Zur Herstellung der Ausführungsbeispiele 7-9 wurden die in Beispiel 5 und 6 beschriebenen Basispasten in den Verhältnissen 20/80, 50/50 und 80/20 mit einem Gesamtgewicht von jeweils 65 g abgewogen. Anschließend wurden die Pasten in den auf 70 °C vortemperierten mit 60 U/min laufenden Laborkneter gegeben und für 120 s gemischt. Anschließend wurde die jeweils entsprechende Menge an TMXDI (2,68 g; 2,93 g; 3,16 g) hinzudosiert. Nach 120 s Reaktionsdauer bei konstanter Temperatur wurde der Kneter mit 20 K/min auf 180 °C geheizt. Während des Heizens reagierten das at PDMS und das TMXDI in Anwesenheit der unterschiedlichen Farbmittel vollständig zu einem Polysiloxan-Harnstoff-Copolymer aus. Bei 180 °C befand sich die gebildete Farb-Masterbatchmatrix im Schmelzezustand. Nach Erreichen der 180 °C wurde das System für weitere 180 s in der Schmelze gemischt und anschließend dem Laborkneter entnommen und auf Raumtemperatur abgekühlt. Die erhaltenen Farb-Masterbatches zeigten abhängig vom Mischungsverhältnis der Basispasten (blau und gelb) verschiedene Grüntöne. Durch nachfolgendes Granulieren wurde ein rieselfähiges, klebfreies Farb-Masterbatch erhalten.For preparing Embodiments 7-9, the base pastes described in Examples 5 and 6 were weighed in ratios of 20/80, 50/50 and 80/20 with a total weight of 65 g each. The pastes were then added to the laboratory kneader running at 60 ° C. at 70 ° C. and mixed for 120 s. Then the appropriate amount of TMXDI (2.68 g, 2.93 g, 3.16 g) was added. After a reaction time of 120 s at constant temperature, the kneader was heated to 180 ° C. at 20 K / min. During heating, the at PDMS and the TMXDI fully reacted to form a polysiloxane-urea copolymer in the presence of the different colorants. At 180 ° C, the color masterbatch matrix formed was in the melt state. After reaching the 180 ° C, the system was mixed in the melt for a further 180 s and then taken from the laboratory kneader and cooled to room temperature. The resulting color masterbatches showed different shades of green depending on the mixing ratio of the base pastes (blue and yellow). Subsequent granulation gave a free-flowing, tack-free color masterbatch.

Claims (17)

Verfahren zur Herstellung eines Farb-Masterbatches mit folgenden Schritten: a) Mischen mindestens einer mit einer Amino-, Hydroxy- oder Carboxy-Gruppe terminierten Siloxanstruktur der allgemeinen Formel I (Komponente A):
Figure imgb0004
 mit R1 unabhängig voneinander ein einwertiger gegebenenfalls durch Fluor oder Chlor substituierter Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, R2 unabhängig voneinander ein Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder einen Arylenrest mit 6 bis 22 Kohlenstoffatomen, X und Y unabhängig voneinander eine Hydroxy-, Carboxy- oder Amino-Gruppe -NR'- mit R' = Wasserstoff, Alkylrest mit 1 bis 10 Kohlenstoffatomen oder Arylrest mit 6 bis 22 Kohlenstoffatomen und n eine Zahl von 1 bis 10000,
mit mindestens einer bifunktionellen Verbindung (Komponente B), die zwei, mit X und Y durch Polyaddition oder Polykondensation verknüpfbare Gruppen aufweist, b) Polymerbildung der Mischung der Komponenten A und B sowie c) Aufschmelzen des Polymerisats im Extruder oder diskontinuierlichen Innenmischer mit anschließender Granulation, dadurch gekennzeichnet,
dass vor Abschluss der Polymerbildung mindestens ein Farbmittel zugesetzt wird. Process for the preparation of a color masterbatch with the following steps: a) mixing at least one amino, hydroxy or carboxy-terminated siloxane structure of the general formula I (component A):
Figure imgb0004
 With R 1 is independently a monovalent hydrocarbon or fluorine radical having 1 to 20 carbon atoms optionally substituted by fluorine or chlorine, R 2 is independently an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O- or an arylene radical having 6 to 22 carbon atoms, X and Y independently of one another hydroxy, carboxy or amino group -NR'- with R '= hydrogen, alkyl radical having 1 to 10 carbon atoms or aryl radical having 6 to 22 carbon atoms and n is a number from 1 to 10000,
with at least one bifunctional compound (component B), the two, with X and Y has groups which can be linked by polyaddition or polycondensation, b) polymer formation of the mixture of components A and B as well c) melting of the polymer in the extruder or discontinuous internal mixer with subsequent granulation, characterized,
that at least one colorant is added before completion of the polymer formation. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass das mindestens eine Farbmittel vor oder während Schritt a) und/oder während Schritt b) zugesetzt wird, insbesondere durch Einmischen und/oder durch Extrusion.Method according to claim 1,
characterized in that the at least one colorant is added before or during step a) and / or during step b), in particular by mixing in and / or by extrusion. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass 1 bis 80 Gew.-%, bevorzugt 10 bis 50 Gew.-%, bezogen auf das Gewicht des gebildeten Polymers, des mindestens einen Farbmittels zugegeben wird.Method according to one of the preceding claims,
characterized in that 1 to 80 wt .-%, preferably 10 to 50 wt .-%, based on the weight of the polymer formed, of the at least one colorant is added. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass das bifunktionale Monomer (Komponente B) ausgewählt ist aus der Gruppe bestehend aus Diisocyanaten, Diaminen, Diolen, Dicarbonsäuren, Diformaldehydterminierten Verbindungen und Mischungen hiervon, insbesondere ein Diisocyanat der allgemeinen Formel II:

        O=C=N-R3-N=C=O     (II)

mit
R3 ein gegebenenfalls durch Fluor oder Chlor substituierter Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen.Method according to one of the preceding claims,
characterized in that the bifunctional monomer (component B) is selected from the group consisting of diisocyanates, diamines, Diols, dicarboxylic acids, Diformaldehydterminierten compounds and mixtures thereof, in particular a diisocyanate of general formula II:

O = C = NR 3 -N = C = O (II)

With
R 3 is an optionally substituted by fluorine or chlorine alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass die Farbmittel ausgewählt sind aus der Gruppe bestehend aus Pigmenten, Farbstoffen und Mischungen hiervon.Method according to one of the preceding claims,
characterized in that the colorants are selected from the group consisting of pigments, dyes and mixtures thereof. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass unmittelbar nach Schritt a) zu dem Zwischenprodukt der Komponenten A und B mindestens ein Kettenextender (Komponente C) mit der allgemeinen Formel III:

        H-V-R4-W-H     (III)

mit
R4 ein gegebenenfalls durch Fluor, Chlor, C1-C6-Alkyl- oder C1-C6-Alkylester substituierter Alkylenrest mit 1 bis 700 C-Atomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O-, -COO-, -OCO- oder -OCOO- ersetzt sein können, und
V, W unabhängig voneinander -O- oder -NR5-, wobei R5 Wasserstoff, ein Alkylrest mit 1 bis 10 C-Atomen oder ein Arylrest mit 6 bis 22 C-Atomen ist,
zugesetzt wird.Method according to one of the preceding claims,
characterized in that immediately after step a) to the intermediate of components A and B at least one chain extender (component C) having the general formula III:

HVR 4 -WH (III)

With
R 4 is an optionally substituted by fluorine, chlorine, C 1 -C 6 alkyl or C 1 -C 6 alkyl ester alkylene radical having 1 to 700 carbon atoms, in which non-adjacent methylene units by groups -O-, -COO- , -OCO- or -OCOO- may be replaced, and
V, W independently of one another are -O- or -NR 5 -, where R 5 is hydrogen, an alkyl radical having 1 to 10 C atoms or an aryl radical having 6 to 22 C atoms,
is added. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass in Schritt a) und/oder Schritt c) weitere Additive ausgewählt aus der Gruppe bestehend aus Nanofüllstoffen, Stabilisatoren, Antistatika, Flammschutzmittel, Haftvermittler, Nukleierungsmittel, Treibmittel, antibakterielle Mittel und Mischungen hiervon zugesetzt werden.Method according to one of the preceding claims,
characterized in that in step a) and / or step c) further additives selected from the group consisting of nanofillers, stabilizers, antistatic agents, flame retardants, adhesion promoters, nucleating agents, blowing agents, antibacterial agents and mixtures thereof are added. Verfahren nach dem vorhergehenden Anspruch,
dadurch gekennzeichnet, dass die Additive in einem Gewichtsanteil zwischen 1 und 80 Gew.-%, bezogen auf das Gewicht des gebildeten Polymers, zugesetzt werden.Method according to the preceding claim,
characterized in that the additives are added in a proportion by weight of between 1 and 80% by weight, based on the weight of the polymer formed. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass die Verbindungen der allgemeinen Formel I (Komponente A) und die bifunktionale Verbindung (Komponente B) in äquimolaren Verhältnissen eingesetzt werden.Method according to one of the preceding claims,
characterized in that the compounds of the general formula I (component A) and the bifunctional compound (component B) are used in equimolar proportions. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass das Verfahren unter Ausschluss von Feuchtigkeit und unter Schutzgas, insbesondere Stickstoff und Argon, durchgeführt wird.Method according to one of the preceding claims,
characterized in that the method under Exclusion of moisture and under inert gas, in particular nitrogen and argon, is performed. Farb-Masterbatch herstellbar nach einem der vorhergehenden Ansprüche.Color masterbatch producible according to one of the preceding claims. Farb-Masterbatch, enthaltend ein Blockcopolymer der allgemeinen Formel IV
Figure imgb0005
 mit R1 unabhängig voneinander ein einwertiger gegebenenfalls durch Fluor oder Chlor substituierter Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, R2 unabhängig voneinander ein Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O-ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen, R3 ein gegebenenfalls durch Fluor oder Chlor substituierter Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen B, B': eine reaktive oder nicht reaktive Endgruppe, welche kovalent an das Polymer gebunden ist, n: eine Zahl von 1 bis 10000 und a: eine Zahl von mindestens 1, sowie mindestens ein Farbmittel. Color masterbatch containing a block copolymer of the general formula IV
Figure imgb0005
 With R 1 is independently a monovalent hydrocarbon or fluorine radical having 1 to 20 carbon atoms optionally substituted by fluorine or chlorine, R 2 independently of one another an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O-substituted groups or an arylene radical having 6 to 22 carbon atoms, R 3 is an optionally substituted by fluorine or chlorine alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms B, B ': a reactive or non-reactive end group which is covalently bonded to the polymer, n: a number from 1 to 10,000 and a: a number of at least 1, and at least one colorant. Farb-Masterbatch, enthaltend ein Blockcopolymer der allgemeinen Formel V
Figure imgb0006
 mit R1 unabhängig voneinander ein einwertiger gegebenenfalls durch Fluor oder Chlor substituierter Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, R2 unabhängig voneinander ein Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O-ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen, R3 ein gegebenenfalls durch Fluor oder Chlor substituierter Alkylenrest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O- ersetzt sein können oder ein Arylenrest mit 6 bis 22 Kohlenstoffatomen, R4 ein gegebenenfalls durch Fluor, Chlor, C1-C6-Alkyl- oder C1-C6-Alkylester substituierter Alkylenrest mit 1 bis 700 C-Atomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -O-, -COO-, -OCO- oder -OCOO- ersetzt sein können, V, W unabhängig voneinander -O- oder -NR5-, wobei R5 Wasserstoff, ein Alkylrest mit 1 bis 10 C-Atomen oder ein Arylrest mit 6 bis 22 C-Atomen ist, B, B': eine reaktive oder nicht reaktive Endgruppe, welche kovalent an das Polymer gebunden ist, n: eine Zahl von 1 bis 10000, a: eine Zahl von mindestens 1, sowie mindestens ein Farbmittel. Color masterbatch containing a block copolymer of the general formula V
Figure imgb0006
 With R 1 is independently a monovalent hydrocarbon or fluorine radical having 1 to 20 carbon atoms optionally substituted by fluorine or chlorine, R 2 independently of one another an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by -O-substituted groups or an arylene radical having 6 to 22 carbon atoms, R 3 is an optionally substituted by fluorine or chlorine alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O- or an arylene radical having 6 to 22 carbon atoms, R 4 is an optionally substituted by fluorine, chlorine, C 1 -C 6 alkyl or C 1 -C 6 alkyl ester alkylene radical having 1 to 700 carbon atoms, in which non-adjacent methylene units by groups -O-, -COO- , -OCO or -OCOO- may be replaced, V, W are independently -O- or -NR 5 -, wherein R 5 is hydrogen, an alkyl radical having 1 to 10 C atoms or an aryl radical having 6 to 22 carbon atoms, B, B ': a reactive or non-reactive end group which is covalently bonded to the polymer, n: a number from 1 to 10,000, a: a number of at least 1, and at least one colorant. Polymerwerkstoff enthaltend den Farb-Masterbatch nach Anspruch 11 bis 13.Polymer material containing the color masterbatch according to claims 11 to 13. Polymerwerkstoff nach Anspruch 14,
dadurch gekennzeichnet, dass der Polymerwerkstoff ausgewählt ist aus der Gruppe bestehend aus Thermoplasten, thermoplastischen Elastomeren, Elastomeren, Duromeren und/oder Copolymeren oder Blends hiervon, insbesondere Polyethylen, Polypropylen, Polyamid, Polyethylenterephthalat, Polybutylenterephthalat, thermoplastische Elastomere auf Basis von vernetztem Kautschuk, Ethylen-Vinylacetat, Polyhydroxybutyrat und/oder Copolymeren oder Blends hiervon.Polymer material according to claim 14,
characterized in that the polymer material is selected from the group consisting of thermoplastics, thermoplastic elastomers, elastomers, thermosets and / or copolymers or blends thereof, in particular polyethylene, polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate, thermoplastic elastomers based on cross-linked rubber, ethylene Vinyl acetate, polyhydroxybutyrate and / or copolymers or blends thereof. Polymerwerkstoff nach einem der Ansprüche 14 oder 15,
dadurch gekennzeichnet, dass der Polymerwerkstoff in Form eines durch formgebende Prozesse, insbesondere Spritzgießen, Extrudieren, Formpressen, Walzenrotation, Rotationsformen, Lasersintern, FDM, Granulieren und/oder Gießen, erhältlichen Formkörpers vorliegt.Polymer material according to one of claims 14 or 15,
characterized in that the polymer material is in the form of a molding obtainable by molding processes, in particular injection molding, extrusion, compression molding, roll rotation, rotational molding, laser sintering, FDM, granulation and / or casting. Verwendung des Farb-Masterbatches nach einem der Ansprüche 11 bis 13 zur Einfärbung von Polymerwerkstoffen.Use of the color masterbatch according to one of Claims 11 to 13 for coloring polymeric materials.
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